|Publication number||US4814000 A|
|Application number||US 06/902,131|
|Publication date||Mar 21, 1989|
|Filing date||Sep 2, 1986|
|Priority date||Aug 13, 1982|
|Also published as||DE3368176D1, EP0102003A1, EP0102003B1|
|Publication number||06902131, 902131, US 4814000 A, US 4814000A, US-A-4814000, US4814000 A, US4814000A|
|Inventors||Baldo Ciocca, Attilio Formigoni, Gino Epis|
|Original Assignee||S.I.P.C.A.M. S.p.A - Societa Italiana Prodotti Chimici e per l'Agricoltura Milano|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (11), Non-Patent Citations (2), Referenced by (4), Classifications (8), Legal Events (4)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This application is a continuation-in-part of application Ser. No. 750,254 filed July 1, 1985 which in turn is a continuation-in-part of application Ser. No. 521,836 filed Aug. 10, 1983, now abandoned.
This invention relates to a chemically stabilised herbicide composition based on meta-biscarbamates.
It is known that herbicide composition containing a compound of formula: ##STR2## or 3-methoxycarbonyl-aminophenyl-N-(3-methylphenyl)carbamate possess excellent herbicide action on sugar beet and other crops, if formulated with suitable adjuvants and inerts.
However, it is also known that the aforesaid compounds possess limited chemical stability with time if prepared in common emulsifiable liquid herbicide compositions based on organic solvents, and which contain adjuvants having no stabilising effect.
U.S. Pat. No. 3,898,075 describe the possibility of stabilising the compoundof formula (A) in emulsifiable liquid herbicide compositions based on organic solvents, by adding a chemical stabilising compound chosen from dicarboxylic aliphatic acids, hydrocarboxylic aliphatic acids, nitro-substituted monocarboxylic aromatic acids, dicarboxylic aromatic acids, sulphonated aliphatic acids, and sulphonated aromatic acids. In addition to claiming these stabilisers, the aforesaid U.S. Patent described the already known addition of common surfactants and inerts commonly used by the expert in this field for preparing emulsifiable liquid composition suitable for use as plant protection products.
Specifically, stated suitable inerts are solvents based on aromatic hydrocarbons, cyclohexanone, isophorone, methylhexahydronaphtalene, dibutylphthalate, tetrahydrophthalene, dimethylsulphoxide and dimethylformamide, and stated suitable surfactants not acting as chemical stabilizers are polyethoxylated amines, alcohols, acids and alkylphenols, and salts of alkylbenzene and naphthalenesulphonic acids.
With the present invention, it has been unexpectedly found that the compound of formula ##STR3## formulated as emulsifiable liquid, can be chemically stabilized with the addition to the formulation of tri-styryl-phenol-phosphates polyethoxylated and/or polypropoxylated, containing 6-25 moles of ethylene oxide and/or propylene oxide (in ratio of from 10:1 to 1:1 if both oxides are present).
Examples of the aforesaid stabilizers, which are usable in organic solvent-based emulsifiable liquid formulations are:
1. tristyril-phenol-phosphates-polyethoxylated with 17 moles of ethylene oxide (available commercially for example under the names SOPROPHOR 3D33 or SOPRAL 3D 33 or Messrs. SOPROSOIE CO. of Rochetaillee, France, or under the name SOITEM 8 FL of Messrs. SOITEM CO. Milan, Italy);
2. Tristyryl-phenol-phosphate-polyethoxylated with 6 moles of ethylene oxide (available commercially as SOITEM 3 FL of Messrs. SOITEM CO., Milan, Italy).
3. Tristyryl-phenol-phosphate-polypropoxylated with 25 moles of propylene oxide (available commercially as SOITEM 25 P of SOITEM CO. Milan, Italy).
4. A mixture of tristyril phenol phosphates polyethoxylated and polypropoxylated, with 20 moles of ethylene oxyde and 5 moles of propylene oxide (available commercially as SOITEM 8 EP of Messrs. SOITEM CO. Milan, Italy).
With respect to the previous known art, the interest of the present invention is even greater when considering that the tristyryl phenol phosphates polyethoxylated and/or polypropoxylated--cited hereabove--able to exhibit a chemical stabilising effect, also possess the property of acting as surfactants, ie as emulsifying agents, in herbicide formulations of emulsifiable liquids based on compound of formula (A), with obvious saving in adjuvants and greater composition economy.
The discovery was completely unattended because the surfactants used by the prior art for emulsifiable liquid compositions based on compound of formula (A), surfactants that can be eventually used also for increasing the biological activity of the compound of formula (A), are chemically different from those claimed in the present invention and--above all--do not show chemical stabilising activity on emulsifiable liquid compositions of compounds of formula (A) as demonstrated in the Table No. 1.
Additionally, it is known that some inorganic and/or organic acids are not active as stabilizers of emulsifiable liquid compositions of the compound of formula (A) and particularly the phosphoric acid, or acetic acid, do not act as stabilizers, as documented in Table No. 1.
Furthermore phenol derivatives as tristyryl-phenol are not active as stabilizers of compositions of formula (A), as reported also in Table No. 1. To the contrary the tri-styryl-phenol phosphates polyethoxylated and/or polypropylated of the invention are particularly active as stabilizers (see Table No. 1).
TABLE NO. 1__________________________________________________________________________Stabilizing activity of some compounds on the emulsifiable liquidcomposi-tion, having following ingredients:__________________________________________________________________________(1) Active Substance: Compound of formula (A) of 97% purity 172 g(2) Surfactants: as reported, in weight(3) Stabilizers: as reported, in weight(4) Solvent: Isophorone up to 1000 g__________________________________________________________________________ % Decomposition of Compound of formula (A) afterSurfactants Possible Stabilizers T° 1 month 3 months__________________________________________________________________________20% of a mixture None 20° C. 3 10of Polethoxy- 54° C. 30 60lated alkylphenol, +1% of phosphoric acid 20° C. 5 9polyethoxylated 54° C. 30 55fatty acid, and +1% of acetic acid 20° C. 6 12calcium dodecyl 54° C. 33 65benzensulfonate +3,5% of tristyryl-phenol 20° C. 8 14 54° C. 35 733.5% tristyrylphenolphosphate 20° C. <0.1 <0.2polyethoxylated with 17moles of ethylene oxide(according to the invention)+1.5% calcium dodecylbenzene 54° C. <0.5 <1sulfonate9.5% tristyrylphenolphosphate 20° C. <0.1 <0.2polyethoxylated with 20moles of ethylene oxideand polypropoxylated with5 moles of propylene oxide 54° C. <0.5 <1(according to the invention)15% tristyrylphenolphosphate 20° C. <0.1 <2polypropoxylated with 25moles of propylene oxide 54° C. <0.5 <1(according to the invention)__________________________________________________________________________
It is totally unattended that tri-styryl-phenol-phosphates polyethoxylated, show high stabilizing activity on the compound of formula (A), whereas both trystyrilphenol and phosphoric acid do not show any stabilizing effect.
Moreover, all the stabilisers according to the invention exhibit their activity in relatively small doses, for the most part economical. In this respect, said stabilisers can be added to the compound of formula (A) in a ratio that can be varied between 1:10 and 2.5:1, according to the type of formulation and the concentration of the compound of formula (A). In addition to the stabilisers, with possible surfactant effect according to the invention, other surfactants, suspending agents or emulsifying agents can be added to formulations of the compound of formula (A), as necessary for optimising the hydrophilic/lipophilic balance of the composition in accordance with the methods well known to the skilled man of the art (for example calcium alkylarylsulphonate, polyethoxylated fatty acids, polyethoxylated alkylarylphenols and others, as described in the publication McCutcheon's--Detergent & Emulsifiers--1982 Annual--International Edition, Glen Rock (N.J.) U.S.A.).
Other active pesticides or adjuvant substances can also be added to the formulations according to the invention, in particular other herbicides, such as chloridazon, metamitron, ethofumesate, lenacil, cycloate, diallate, triallate, butachlor, metolachlor, trimexachlor and others. For organic solvent-based liquid formulations which are emulsifiable in water, the following composition can be used by way of example:
10-25% (preferably 15-20%) of active substance of formula (A);
1-25% (preferably 2-10%) of stabiliser, which may also possess emulsifying action, possibly together with a further surfactant not possessing stabilising activity.
Remainder to 100% of solvents, together with other emulsifiers, if necessary. The solvents used can be isophorone, cyclohexanone, aromatic hydrocarbons, naphta solvent, dimethylsulphoxide, dimethylformamide, N-methylpyrrolidone and others.
The composition according to the invention is particularly suitable for use in the selective weed control of agricultural or horticultural crops (such as sugar beet, fodder beet, red beet, spinach, strawberries, etc.) mainly in treatment after weeds emergence, by spraying dilute aqueous emulsions or suspension containing from 0.23 to 1.5 Kg/Ha of active substance.
The following examples are useful for better illustrating the invention, but do not limit its possible applications.
The following substance are fed into a vessel fitted with a liquid stirrer, and are kept constantly mixed:
______________________________________ Formula I Formula II______________________________________Compound of formula (A) with 97% 17.2 Kg. 17.2 Kg.puritySOITEM 8 FL (1) 7.0 Kg. 1.7 Kg.Calcium dodecylbenzenesulphonate 3.0 Kg. 1.0 Kg.Naphta solvent 3.0 Kg. 10.0 Kg.Isophorone 69.8 Kg. 70.1 Kg.TOTAL 100.0 Kg. 100.0 Kg.______________________________________
______________________________________ Formula III Formula IV______________________________________Compound of formula (A) with 97% 17.2 Kg. 17.2 Kg.puritySOPROPHOR 3D33 (2) 3.5 Kg. 20.0 Kg.SOITEM 101 (I) 0.5 Kg. 1.0 Kg.SOITEM 990 (1) 2.0 Kg. 3.0 Kg.Naphta solvent 3.0 Kg. --Isophorone 73.8 Kg. 58.8 Kg.TOTAL 100.0 Kg. 100.0 Kg.______________________________________
______________________________________ Formula V Formula VI______________________________________Compound of formula (A) with 97% 11.8 25.5puritySOITEM 8 EP (1) 17.7 --SOITEM 3 FL (I) -- 7.5SOITEM 101 (1) 0.5 2.0SOITEM 990 (1) 3.5 3.0Naphta solvent 3.0 3.0Isophorone 63.5 59.0TOTAL 100.0 100.0______________________________________
Various stabilized emulsifiable liquid formulations are thereby obtained, to be used as herbicides.
(1) Messrs. SOITEM Milan (Italy)
(2) Messrs. SOPROSOIE Rochetaillee (France)
The chemical stability of the active substance is observed at various temperature levels (20° C., and 54° C.) for various lengths of time (1 month and 3 months) for organic solvent-based emulsifiable liquid formulations, according to the invention, as indicated in Example No. 1, compared with an emulsifiable liquid formulation without stabilisers and having the following composition:
______________________________________Compound of formula (A) with 97% purity 17.2 Kg.SOITEM 101 (mixture of 80% octylphenol polyethoxy- 1.0 Kg.lated with 20 moles E.O. with 20% calcium dodecyl-benzenesulfonate).sup.(1)SOITEM 990 (mixture of 25% octylphenol polyethoxy- 7.0 Kg.lated with 20 moles E.O. with 75% calcium dodecyl-benzenesulfonate).sup.(1)Isophorone 74.8 Kg.TOTAL 100.0 Kg.______________________________________ .sup.(1) Produced by SOITEM, Milan (Italy)
After the aging test of 3 months the formulation samples were used in a field with sugar beets of variety Monogem as post-emergence herbicides at the dosage of 2 and 6 l/ha, there being present a mixed population of weeds represented in almost equal proportion by Chenopodium album, Stellaria media, Capsella bursa-pastoris, Solanum nigrum, in a young stage of growth.
Three weeks after the herbicidal treatments the percent reduction of treated weeds was compared to the percent reduction of untreated weeds. No damage to sugar beets with both rates of herbicides was observed. Such results were also reported in the Table No. 1.
From the results shown in Table No. 1, it can be seen that the addition of the chemical stabilisers, according to the invention, prevents the decomposition of the active substance and loss of good herbicidal activity of the formulations, even if the emulsifiable liquid formulation is kept at elevated temperature for a long period.
TABLE NO. 1__________________________________________________________________________Stability of the active substance of formula (A) (3-methoxycarbonyl-amino-phenyl-N-(3-methylphenyl) carbamate) in emulsifiable liquidcompositions,without and with chemical stabilisers according to the invention, after 1monthand 3 months of aging at 20° C. or 54° C. and theiractivity as post-emergenceherbicides after 3 months of aging. % Activity on % Decomp. active weeds after % Damages substance after 3 months at on SugarCOMPOSITIONS T° 1 month 3 months 6 l/ha 2 l/ha beets__________________________________________________________________________Composition with stabiliser 20° C. <0.1 <0.2 100 90 0Formula I (Example No. 1) 54° C. <0.3 <1 99 82 0Composition with stabiliser 20° C. <0.1 <0.2 99 88 0Formula II (Example No. 1) 54° C. <0.5 <1 97 80 0Composition with stabiliser 20° C. <0.1 <0.2 99 89 0Formula III (Example No. 1) 54° C. <0.5 <2 98 82 0Composition with stabiliser 20° C. <0.1 <0.2 100 92 0Formula IV (Example No. 1) 54° C. <0.3 <1 98 86 0Composition with stabiliser 20° C. <0.1 <0.2 95 82 0Formula V (Example No. 1) 54° C. <0.3 <1 92 78 0Composition with stabiliser 20° C. <0.1 <0.2 100 96 0Formula VI (Example No. 1) 54° C. <0.5 <2 100 95 0Composition without stabiliser 20° C. 3 <10 60 20 0Formula of (Example No. 2) 54° C. 30 <60 25 5 0__________________________________________________________________________ Formula I with stabiliser is a preferred composition.
The results are shows in Table No. 2, from which it can be seen that the addition of the stabilisers, according to the invention, prevents the decomposition of the active substance, even if the emulsifiable liquid formulation is kept at elevated temperature for a long period.
TABLE NO. 2______________________________________Stability of the active substance of formula (A) (3-methoxycarbonyl-aminophenyl-N--(3-methylphenyl) carbamate) in emulsifiableliquid compositions, with and without stabilisers accordingto the invention. % Decomposition active substance afterCOMPOSITIONS T° 1 month 3 months______________________________________Composition with stabiliser 20° C. <0.1 <0.2Formula I (Example No. 1) 54° C. <0.3 <1Composition with stabiliser 20° C. <0.1 <0.2Formula II (Example No. 1) 54° C. <0.5 <1Composition with stabiliser 20° C. <0.1 <0.2Formula III (Example No. 1) 54° C. <0.5 <2Composition with stabiliser 20° C. <0.1 <0.2Formula IV (Example No. 1) 54° C. <0.3 <1Composition with stabiliser 20° C. <0.1 <0.2Formula V (Example No. 1) 54° C. <0.3 <1Composition with stabiliser 20° C. <0.1 <0.2Formula VI (Example No. 1) 54° C. <0.5 <2Composition without stabiliser 20° C. 3 <10Formula of (Example No. 2) 54° C. 30 <60______________________________________
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3404975 *||Nov 15, 1965||Oct 8, 1968||Fmc Corp||m-(carbamoyloxy)-carbanilates as herbicides|
|US3898075 *||Jul 3, 1972||Aug 5, 1975||Czyzewski Alfred||Stabilized liquid compositions|
|US4202684 *||Aug 24, 1978||May 13, 1980||Schering Aktiengesellschaft||Carbanilic acid esters, process for making the same and herbicidal compositions containing same|
|US4252557 *||Jun 11, 1979||Feb 24, 1981||Schering Aktiengesellschaft||M-diurethanes|
|US4257804 *||Apr 10, 1979||Mar 24, 1981||Schering Aktiengesellschaft||Carbamic acid ester, process for making the same and composition containing same|
|US4313847 *||May 25, 1979||Feb 2, 1982||Ici Americas Inc.||Surfactant compositions|
|US4315769 *||Nov 21, 1979||Feb 16, 1982||Schering Ag||Herbicidaldiurethanes and their use|
|US4441915 *||Jul 15, 1981||Apr 10, 1984||Schering Aktiengesellschaft||Diurethanes and herbicidal compositions containing the same|
|US4461641 *||Feb 25, 1982||Jul 24, 1984||Ciba-Geigy Corporation||Herbicidal mixtures|
|GB1193998A *||Title not available|
|JPS5758601A *||Title not available|
|1||Bachelot et al., "Aqueous Insecticide, etc.," (1981) CA 95:163933g (1981).|
|2||*||Bachelot et al., Aqueous Insecticide, etc., (1981) CA 95:163933g (1981).|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US5082591 *||May 30, 1989||Jan 21, 1992||Rhone-Poulenc Chimie||Surface active agent based on polyoxyalkylenated (1-phenyl ethyl) phenols, the process for preparation thereof and the use thereof for producing emulsifiable concentrated solutions of active materials|
|US5770760 *||Apr 2, 1996||Jun 23, 1998||Rhodia Inc.||Polymers useful as pH responsive thickeners and monomers therefor|
|US5874495 *||Jun 7, 1995||Feb 23, 1999||Rhodia Inc.||Polymers useful as PH responsive thickeners and monomers therefor|
|US6455471 *||Feb 8, 1999||Sep 24, 2002||Syngenta Crop Protection, Inc.||Pesticidal compositions|
|U.S. Classification||504/301, 504/363|
|International Classification||A01N25/22, A01N47/22|
|Cooperative Classification||A01N47/22, A01N25/22|
|European Classification||A01N47/22, A01N25/22|
|Nov 21, 1986||AS||Assignment|
Owner name: S.I.P.C.A.M. S.P.A. - SOCIETA ITALIANA PRODOTTI CH
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:CIOCCA, BALDO;FORMIGONI, ATTILIO;EPIS, GINO;REEL/FRAME:004632/0961
Effective date: 19860926
Owner name: S.I.P.C.A.M. S.P.A. - SOCIETA ITALIANA PRODOTTI CH
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CIOCCA, BALDO;FORMIGONI, ATTILIO;EPIS, GINO;REEL/FRAME:004632/0961
Effective date: 19860926
|Oct 21, 1992||REMI||Maintenance fee reminder mailed|
|Mar 21, 1993||LAPS||Lapse for failure to pay maintenance fees|
|Jun 8, 1993||FP||Expired due to failure to pay maintenance fee|
Effective date: 19930321